Heterocyclic compounds

ABSTRACT

A heterocyclic compound has the following formula (I)wherein Y represents a substituted or unsubstituted ethylene group or a trimethylene group, W represents the group -SO2R1, X represents an oxygen atom or sulfur atom or the group -NR2 or -CHR3, R represents a hydrogen atom or a methyl group and Z represents a pyridyl group.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to heterocyclic compounds useful as pesticides.

2. Description of the Related Art

U.S. Pat. No. 4,742,060 discloses a heterocyclic compound of the formula

wherein n=0 or 1; X=S, O, —N—R₇ or —CH—R₈; Y=N or C—R₉; R₇, R₈,R₉=hydrogen or specific organic radicals; Z=5- or 6-memberednitrogen-containing heterocyclic ring; R₁, R₂, R₅, R₆=hydrogen or alkylgroup; R₃, R₄=hydrogen, hydroxy group or alkyl group.

U.S. Pat. No. 4,849,432 discloses a heterocyclic compound that issimilar to the aforementioned heterocyclic compound, except that thegroup —NO₂ is replaced by a —CN group and that Y is a nitrogen atom.

The above heterocyclic compounds are useful as pesticides.

The disclosures of the aforementioned U.S. patents are incorporatedherein by reference in their entirety.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide novel heterocycliccompounds that are useful as pesticides.

According to the present invention, a heterocyclic compound has thefollowing formula (I):

wherein Y represents a substituted or unsubstituted ethylene group ortrimethylene group, W represents the group —SO₂R₁, in which R₁represents a hydrogen atom, a C₁-C₄alkyl group, a C₁-C₄ alkoxy group, aC₂-C₄ alkenyl group, or an aryl group, X represents an oxygen or sulfuratom or the group —NR₂ or —CHR₃, in which R₂ represents a hydrogen atom,a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkylthio group, aC₂-C₄ alkenyl group, an alkylcarbonyl group, an alkylsulfonyl group, apyridylmethyl group, a benzyl group, a formyl group, a phenylcarbonylgroup, a phenoxycarbonyl group, or a phenylsulfonyl group, and in whichR₃ represents a hydrogen atom or a C₁-C₇ alkyl group, R represents ahydrogen atom or a methyl group, and Z represents a pyridyl groupoptionally substituted by at least one substituent selected from agroupconsisting of halogen atoms, C₁-C₄ alkyl groups, C₂-C₄ alkenyl groups,C₁-C₄ alkoxy groups, C₁-C₄ alkylcarbonyl groups, C₁-C₄ alkylthio groups,C₁-C₄ haloalkyl groups, C₁-C₄ haloalkoxy groups, C₁-C₄ alkylsulfonylgroups, a cyano group, and a nitro group.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention relates to a novel heterocyclic compound that hasthe following formula (I):

wherein Y represents a substituted or unsubstituted ethylene group ortrimethylene group, W represents the group —SO₂R₁, in which R₁represents a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, aC₂-C₄ alkenyl group, or an aryl group, X represents an oxygen or sulfuratom or the group —NR₂ or —CHR₃, in which R₂ represents a hydrogen atom,a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkylthio group, aC₂-C₄ alkenyl group, an alkylcarbonyl group, an alkylsulfonyl group, apyridylmethyl group, a benzyl group, a formyl group, a phenylcarbonylgroup, a phenoxycarbonyl group, or a phenylsulfonyl group, and in whichR₃ represents a hydrogen atom or a C₁-C₇ alkyl group, R represents ahydrogen atom or a methyl group, and Z represents a pyridyl groupoptionally substituted by at least one substituent selected from a groupconsisting of halogen atoms, C₁-C₄ alkyl groups, C₂-C₄ alkenyl groups,C₁-C₄ alkoxy groups, C₁-C₄ alkylcarbonyl groups, C₁-C₄ alkylthio groups,C₁-C₄ haloalkyl groups, C₁-C₄ haloalkoxy groups, C₁-C₄ alkylsulfonylgroups, a cyano group, and a nitro group.

The heterocyclic compounds of formula (I) of this invention are found tobe very effective against insects and are applicable for use in theagriculture industry.

The following Examples illustrate preparation of the heterocycliccompound of formula (I)

EXAMPLE 1

1.2 g of 2-[(4-methylphenyl)sulfonylimino] imidazolidine was dissolvedin 30 ml of dry dimethylformamide. The mixture was subsequently addedwith 0.25 g of 60% sodium hydride at room temperature, and was stirredfor 1 hour to form sodium salt of imidazolidine. The reaction mixturewas added with 0.81 g of 6-chloro-3-chloromethylpyridine (CCMP) at roomtemperature, and was stirred for 3 hours. After the reaction, theremaining dimethylformamide was removed, and 15 ml of ice water anddichloromethane were added to the mixture. Dichloromethane was distilledoff from the dichloromethane phase in the mixture to yield a yellowishsolid. The yellowish solid was purified by known recrystallizationtechniques to yield 1.29 g white crystals of3-(2-chloro-5-pyridylmethyl)-2-[(4-methylphenyl)sulfonylimino]imidazolidine.The thus formed crystals have a melting point in a range of from 178.5to 179.2° C.

EXAMPLES 2-6

Example 1 was repeated, except that the reactant2-[(4-methylphenyl)sulfonylimino]imidazolidine was replaced by anequivalent amount of2-[(4-methylphenyl)sulfonylimino]tetrahydropyrimidine for Example 2, 2-[methylsulfonylimino]imidazolidine for Example 3,2-[methylsulfonylimino]tetrahydropyrimidine for Example 4,2-[(4-chlorophenyl)sulfonylimino]imidazolidine for Example 5, and2-[(4-chlorophenyl)sulfonylimino]tetrahydropyrimidine for Example 6. Thefinal products for the Examples 2 to 6 are respectively3-(2-chloro-5-pyridylmethyl)-2-[(4-methylphenyl)sulfonylimino]tetrahydropyrimidine,3-(2-chloro-5-pyridylmethyl)-2-[methylsulfonylimino] imidazolidine,3-(2-chloro-5-pyridylmethyl)-2-[methylsulfonylimino]tetrahydropyrimidine,3-(2-chloro-5-pyridylmethyl)-2-[(4-chlorophenyl)sulfonylimino]imidazolidine,and3-(2-chloro-5-pyridylmethyl)-2-[(4-chlorophenyl)sulfonylimino]tetrahydropyrimidine.

EXAMPLE 7

A mixture of 1.62 g of 6-chloro-3-chloromethyl pyridine (CCMP), 2.56 gof 2-[(4-methylphenyl) sulfonylimino]thiazolidine, 3.0 g of potassiumcarbonate, and 50 ml acetonitrile was heated under reflux for 3 hours.After the reaction, the product in the reaction mixture was purified byknown crystallization techniques to yield pale yellowish crystals of3.51 g3-(2-chloro-5-pyridylmethyl)-2-[(4-methylphenyl)sulfonylimino]thiazolidine.The thus formed crystals have a melting point in a range of from 162.1to 162.8° C.

EXAMPLES 8 TO 12

Example 7 was repeated, except that the reactant2-[(4-methylphenyl)sulfonylimino]thiazolidine employed in Example 7 wasreplaced by an equivalent amount of2-[(4-methylphenyl)sulfonylimino]oxazolidine for Example 8,2-[methylsulfonylimino]thiazolidine for Example 9,2-[methylsulfonylimino]oxazolidine for Example 10, 2-[(4-chlorophenyl)sulfonylimino]thiazolidine for Example 11, and 2-[(4-chlorophenyl)sulfonylimino]oxazolidine for example 12. The final products for theExamples 8 to 12 were respectively3-(2-chloro-5-pyridylmethyl)-2-[(4-methylphenyl)sulfonylimino]oxazolidine,3-(2-chloro-5-pyridylmethyl)-2-[methylsulfonylimino]thiazolidine,3-(2-chloro-5-pyridylmethyl)-2-[methylsulfonylimino]oxazolidine,3-(2-chloro-5-pyridylmethyl)-2- [(4-chlorophenyl)sulfonylimino]thiazolidine, and3-(2-chloro-5-pyridylmethyl)-2-[(4-chlorophenyl)sulfonylimino]oxazolidine.

Table 1 lists the formula and the melting point of the final product ofeach of the aforesaid Examples.

TABLE 1 Melting Example formula point, ° C. 1

178.5-179.2 2

155.2-156.0 3

130.2-130.9 4

153.9-154.6 5

178.3-179.7 6

151.7-152.5 7

162.1-162.8 8

153.5-154.2 9

143.9-144.6 10

— 11

164.8-165.2 12

156.1-157.3

BIOLOGICAL TEST ON APHID EXAMPLE 13

9.6 g of the compound (based on the active ingredient) obtained fromExample 1 was blended with 90.4 g of a solvent to form a 9.6% w/wpesticide reagent An 8 cm×8 cm piece of cabbage leaf was placed on alump of wetted cotton in each one of four Petri dishes. 20 aphids weresubsequently put on the cabbage leaf in each one of the Petri dishes.The thus formed pesticide reagent was diluted 1000 times with water toform a diluted solution which was then sprayed onto the cabbage leaf ineach one of the Petri dishes in a predetermined amount. The number ofdead aphids in each one of the Petri dishes was examined after 24 hours.

EXAMPLES 14 TO 24

Example 13 was repeated, except that the compound employed in Example 13was replaced by the compound obtained from a respective one of theExamples 2 to 12.

COMPARATIVE EXAMPLE 1

Example 13 was repeated, except that the compound employed in Example 13was replaced by imidachloprid which is a heterocyclic compound of theformula disclosed in U.S. Pat. No. 4,742,060.

Table 2 lists the effectiveness of the pesticide reagents prepared inExamples 13 to 24 and the Comparative Example 1.

TABLE 2 Number of dead aphids Effecti Example 1st 2nd 3rd 4th averageveness* blank  0  0  1  0 0.25 — 13 15 18 16 17 16.5 82.28 14 16 17 1716 16.5 82.28 15 16 18 19 19 18 89.87 16 17 17 19 19 18 89.87 17 20 1819 20 19.25 96.20 18 19 19 19 17 18.5 92.41 19 17 16 18 17 17 84.81 2017 16 18 15 16.5 82.28 21 16 18 19 18 17.75 88.61 22 18 16 19 17 17.587.34 23 18 18 16 18 17.5 87.34 24 15 18 19 19 17.75 88.61 Comparative18 17 18 16 17.25 86.08 Example 1 *A higher value of effectivenessindicates greater effectivity for the pesticide reagent.

The above biological test results show that the heterocyclic compoundsof formula (I) of this invention exhibit excellent pesticide function.

With the invention thus explained, it is apparent that variousmodifications and variations can be made departing from the spirit ofthe present invention. It is therefore intended that the invention belimited only as recited in the appended claims.

We claim:
 1. A heterocyclic compound having the following formula (I):

wherein: Y represents an ethylene group, W represents the group —SO₂R₁,in which R₁ represents a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄alkoxy group, a C₂-C₄ alkenyl group, or an aryl group, X represents anoxygen or sulfur atom or the group —NR₂ or —CHR₃, in which R₂ representsa hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a C₁-C₄alkylthio group, a C₂-C₄ alkenyl group, an alkylcarbonyl group, analkylsulfonyl group, a pyridylmethyl group, a benzyl group, a formylgroup, a phenylcarbonyl group, a phenoxycarbonyl group, or aphenylsulfonyl group, and in which R₃ represents a hydrogen atom or aC₁-C₇ alkyl group, R represents a hydrogen atom or a methyl group, and Zrepresents a pyridyl group or a substituted pyridyl group whereinsaid-substituents are selected from the group consisting of halogenatoms, C₁-C₄ alkyl groups, C₂-C₄ alkenyl groups, C₁-C₄ alkoxy groups,C₁-C₄ alkylcarbonyl groups, C₁-C₄ alkylthio groups, C₁-C₄, haloalkylgroups, C₁-C₄ haloalkoxy groups, C₁-C₄ alkylsulfonyl groups, a cyanogroup, a nitro group, or mixtures thereof.
 2. The heterocyclic compoundof claim 1, wherein: Y is an ethylene group, W is the group —SO₂CH₃, Xis the group —NH, R is a hydrogen atom, and Z is a 2-chloro-5-pyridylgroup.
 3. The heterocyclic compound of claim 1, wherein: Y is anethylene group, W is the group —SO₂CH₃, X is an oxygen atom, R is ahydrogen atom, and Z is a 2-chloro-5-pyridyl group.
 4. The heterocycliccompound of claim 1, wherein: Y is an ethylene group, W is the group—SO₂ CH₃, X is a sulfur atom, R is a hydrogen atom, and Z is a2-chloro-5-pyridyl group.
 5. The heterocyclic compound of claim 1,wherein: Y is an ethylene group, W is the group —SO₂C₆H₄—CH₃, X is thegroup —NH, R is a hydrogen atom, and Z is a 2-chloro-5-pyridyl group. 6.The heterocyclic compound of claim 1, wherein Y is an ethylene group, Wis the group —SO₂C₆H₄,—CH₃, X is an oxygen atom, R is a hydrogen atom,and Z is a 2-chloro-5-pyridyl group.
 7. The heterocyclic compound ofclaim 1, wherein Y is an ethylene group, W is the group —SO₂C₆H₄—CH₃, Xis a sulfur atom, R is a hydrogen atom, and Z is a 2-chloro-5-pyridylgroup.
 8. The heterocyclic compound of claim 1, wherein: Y is anethylene group, W is the group —SO₂C₆H₄—Cl, X is the group —NH, R is ahydrogen atom, and Z is a 2-chloro-5-pyridyl group.
 9. The heterocycliccompound of claim 1, wherein: Y is an ethylene group, W is the group—SO₂C₆H₄—Cl, X is an oxygen atom, R is a hydrogen atom, and Z is a2-chloro-5-pyridyl group.
 10. The heterocyclic compound of claim 1,wherein Y is an ethylene group, W is the group —SO₂C₆H₄—Cl, X is asulfur atom, R is a hydrogen atom, and Z is a 2-chloro-5-pyridyl group.11. A pesticide reagent comprising an effective amount of theheterocyclic compound of claim
 1. 12. The pesticide reagent of claim 11which further comprises a solvent blended with an effective amount ofthe heterocyclic compound of claim
 1. 13. A method for killing insectscomprising treating plant matter with an effective amount of theheterocyclic compound of claim 1.